Treatment of fibrous materials



Patented Jan. 2, 1940 I UNITED STATES PATENT OFFICE TREATMENT OF FIBROUS MATERIALS Karl Brodersen, Matthias Quaedvlieg, and Max- Zabel, Dessau in Anhalt, and Albert Schneider, Leipzig, Germany, assignors to I. G. Farbenindustr'ie Aktiengesellschaft, Frankfort-on-the- Main, Germany,

No Drawing. Application March 4, 1938, Serial No. 193,850. In Germany March 9, 1937 12 Claims.

The invention is based on the observation that by hydroxyalkylating blguanides of organic bases of high molecular weight valuable products are obtained which have manifold uses. Unexpectedly, the treatment of these biguanides with alkylene oxide produces no splitting but a smooth addition, for example a stearyl biguanide, which, after exposure to ethylene oxide, would be expected to have a molecule of 706, proves to have, as determined by titration with N-hydrochloric acid, a molecule of 69 i. The reaction with alkylene oxides occurs especially at high temperature very easily; if desired, it can be accelerated by the addition of some free caustic alkali.

While the non-hydroxyalkylated biguanides form with the anions, for instance, S04 or PO4 occurring in the usual water supplies as well as with organic acids, especially carboxyllc acids and sulfonic acids of high molecular weight or their. water-soluble salts, compounds which are sparingly soluble, the hydroxyalkylated products yield salts of far better solubility. The solubility rises with a degree of hydroxyalkylation; the highly hydroxyalkylated bodies are in part already soluble in water in the form of free bases. I

The new substances, especially in the form their salts, are characteristic assistants for the improvement of textiles. Even in quite small concentration they impart a soft, full feel to artificial silk, which can be modified in various directions by simultaneous use of other known improving agents, for instance fatty acid amides, fatty alcohols or their sulfonates and fatty acid condensation products. They are also suitable, if desired in combination with the aforesaid additional bodies, for making pastes of dyes, for dispersing pigments or matting artificial silk or mixed fabrics, for levelling and dyeing throughout and for other purposes in the textile, leather and paper industries.

These new textile assistants show in many cases, as do a large number of other compounds proposed for the same purposes, the disadvantage that they change the colortint of dyed material. This is the more disturbing because the treatment with softening agents and even with matting agents occurs in many cases only after the dyeing, so that a. subsequent shading-01f is no longer practicable. It has been proposed to compensate this shifting tint by a subsequent treatment with, for example resin soaps or other compounds which yield an insoluble precipitate with the bases.

An improving agent, which is free from coloristic objection and is highly active, may be obtained, however, if the said bases are used in the form of the soluble salts which they produce, together with organic carboxylic acids or. sulfonic acids. Especially applicable for this purpose are the salicylates, glycollates and lactates which, in contrast with the chlorides do not vary the color tint.

The following examples illustrate the invention, the parts being by weight:

Example 1.100 parts of stearyl biguanide are treated, while stirring, and at a raised temperature, for example 100 to 150 C., with ethylene oxide until 100 to 110 parts have been introduced.

The free base is converted into a. salt, for example a salicylate.

0.2 gram of this salicylate of polyhydroxyethylated stearyl biguanide per liter of liquor imparts to viscose or copper silk a soft feel.

Instead of the sallcylate of the polyhydroxyethylated stearyl biguanide there may be a. corresponding salt of a carboxylic acid or sulfonic acid of high molecular weight.

This softening agent dissolves well in water,

and has the same softening effect as that of the chloride for instance, but in contrast with the latter does not shift the tint of the substantively dyed artificial silk.

Example 2.-100 parts of zinc sulfide or titanium dioxide are made into a paste with the addition of some water or alcohol with 5 parts of a. product made as described in Example 1 and the paste is evaporated on drying rollers; there is thus obtained a powder which is readily convertible into a stable emulsion, of which even 0.5 gram per liter suffices for matting deeply artificial silk, for instance viscose silk, copper silk or acetate silk. The feel of the silk is thereby rendered soft and full.

On dyed material no change of color. is produced. 7

Example 3.Similar effects are obtainable when using a preparation of the following coniposition: i

parts of zinc sulfide, 1.5 parts of stearyl biguanide hydrochloride,- 1.5 parts of the salicylate of polyhydroxyethylated stearyl biguanide and 50 parts ofwater.

Example 4.--50 parts of zinc sulfide are stirred together with 10 parts of the laurate of polyhy-.

droxyethylated stearyl biguanide and 15 parts of water. When treating lustrous viscose silk in a bath prepared with this composition as indicated in the foregoing examples, a good matt effect and a soft full feel of the fabric'is obtained.

The polyhydroxyalkylated biguanides or their salts applicable for improving textiles, for example by matting, produce an especially good effect when used in admixture with alcohols having at least 10 carbon atoms and the carbon chain of which may be interrupted by one or more heteroatoms or atom groups, for instance -O--, -COO- and -CON.R. This definition includes, for example polyalcohols and ethers obtainable by polymerization of ethylene oxide, fatty alcohols and their ethers and esters containing free OH- groups, also esters and amides of soap-forming fatty acids containing free OH- groups. Outstanding examples are stearic acid mono-glyceride, stearylpolyglycol ether, stearic acid polyglycol or polyglycerol ester, lauric acid mono-glycol ester and palmitic acid ethanolamide.

Mixtures of the said compounds with polyhydroxyalkylated biguanides or their salts yield together with suitable pigments, for instance zinc sulfide, titanium dioxide, lithopone, barium sulfate and china clay a very good matting which does not dust on various textiles. The softening effect is very good; the fullness of the yarns and fabrics desirable in many cases may be obtained by suitable choice of the above-named additional components. The satisfactory stability of the treating baths is very noticeable.

Example 5.'70 parts of zinc sulfide are stirred to form a homogeneous paste with 6 parts of the salicylate of polyhydroxyethylated stearyl biguanide, 3 parts of stearic acid mono-glyceride and 0.3 part of stearyl polyglycol ether, as well as 20.7 parts of water. Lustrous viscose silk is treated with 50 times its weight of liquor containing 1 gram per liter of the above mixture, for half an hour, at about 30 C. There is obtained a deep matt effect, and at the same time a soft full feel. The bath is nearly completely exhausted and shows a remarkably good stability.

Example 6,-60 parts of titanium dioxide, 9 parts of the salicylate of the polyhydroxyethylated stearyl biguanide, 3 parts of stearic acid mono-glyceride, 0.2 part of ethylene poly-glycol ether, and 27.8 parts of water are stirred together to form a homogeneous paste. mixture is dispersed in 1 liter of water. In this liquor 20 grams of a mixed fabric from parts of wool and 20 parts of viscose artificial silk is treated for half an hour at 30 to 35 C. The fabric acquires an improved matt appearance and agreeable feel.

Instead of stearic acid mono-glyceride a stearic acid poly-glyceride, likewise, may be used. If desired, paraffine oil or glue may be added to the preparation.

Example ?.25 parts of zinc sulfide, 6 parts of the salicylate of the polyhydroxyethylated stearyl biguanide, 3 parts of lauric alcohol and 6 parts of water are stirred together to form a homogeneous paste. 0.5 gram of this mixture is dispersed in 1 liter of water. When treating viscose silk in this bath at 30 to 35 0., a deep non-a dusting matt effect is obtained and at the same time a soft full feel.

Example 8.A further preparation applicable as indicated in the other examples has the following composition:

50 parts of zinc sulfide, 2.5 parts of the salicyl- 0.3 gram of this ate of polyhydroxyethylated stearyl biguanide, 2.5 parts of a hydroxyethylated stearic acid-3- ethanolamine ester and 15 parts of water.

Example 9.Preparations of our new matting agents likewise may be prepared in a dry form. Thus, 40 parts of china clay, 60 parts of zinc sulfide, 5 parts of the salicylate of polyhydroylated stearyl biguanide, 4 parts of stearic acid polyglyceride and 1 part of a polyhydroxyethylated dodecyl phenol may be intimately mixed together in the presence of methanol and then dried. A powder is obtainable which is easily dispersed for use in water.

The polyhydroxyalkylated biguanides make it possible to combine for example the operation of matting artificial silk with the dyeing process. A mixture of the salts of the polyhydroxyalkylated biguanide with matting pigments, if desired with the addition of one or more of the aforesaid additional components, is introduced into the dye-bath so that dyeing and matting are effected in the same working operation. In this manner troubles which often occur in separated operations are avoided, for instance trouble caused by a shift of tint in consequence of the admixing with white pigment, so that it is not possible to arrive with certainty at a definite tone. In this new mode of working, however, exact coloring of goods becomes possible.

Example 10.60 parts of zinc sulfide are stirred together with 20 parts of a salicylate prepared as described in Example 1 and 20 parts of water to form a homogeneous paste. If 2 grams per liter of this paste are added to the dyeing liquor which has been prepared in the manner usual for artificial silk, preferably without Turkey red oil or similar products, the dyeing obtained is accompanied by a good matt effect and agreeable full soft feel of the goods. The matting obtained is uniform and fast to rinsing.

In the'above examples the treatment of artificial silk is chiefly adopted. The polyhydroxyalkylated biguanides, however, may be used in similar'manner for improving other fibrous materials, for instance natural silk, wool, cotton and other natural fibers, as well as cellulose esters and cellulose ethers.

There may be made, for instance, a preparation of the following composition:

50 parts of zinc sulfide, 10 parts of polyhydroxyethylated stearyl biguanide in the form of its salicylate, 5 parts of a protective colloid, for example dodecyl-phenol-poly-glyco1 ether, 5 parts of a solution of 20 per cent. strength of polymerized vinylmethyl ether as a dressing agent, 5 parts of olive oil and 25 parts of water are mixed together. If a mixed fabric of wool and regenerated cellulose fiber is treated on the Foulard with a padding liquor containing per liter 6 grams of this preparation, if desired with addition of 6 grams of Turkey red oil, there is is obtained an excellent and fast matting.

It is obvious that our invention is not limited to the foregoing examples or to the specific details given therein. In the examples we make use of polyhydroxyethylated stearyl biguanide, there may be used, however, in the same manner polyhydroxyethylated dodecyl biguanide, tetradecyl biguanide, cetyl biguanide, oleyl biguanide and analogous compounds or other polyhydroxyalkyl compounds of the same deriving, for instance, from poly-glycerine. As acids forming water-soluble salts of the said polyhydroxyalkylated biguanides which do not alter the shade of dyed fabrics, there may be mentioned furthermore toluene sulfonic acid, diisobutylnaphthalene sulfonic acid, stearyl sulfonic acid, oleylmethyitauride, dodecyl sulfuric acid ester, tartaric acid, benzoic acid, naphthenic acid.

As a pigment causing the matting eflect, there may be likewise used lithopone or other inorganic or organic colored or white pigments. Other assistants known in the art for improving fabrics, such as starch or sizing compounds, may be added to our treating bath.

What we claim is:

l. The process forjimproving textile; fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyalhlated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with an acid of the group consisting of organic carboxylic acids and organic sulfonic acids.

2. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyethylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with an acid of the group consisting of organic. carboxylic acids and organic sulfonic acids.

3. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyalkylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with a hydroxycarboxylic acid.

4. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroiwethylated blguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with a hydroxycarboxylic acid.

5. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyalkylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid.

6. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyethylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid.

'7. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyalkylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid, and a pigment.

8. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyethylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid, and a pigment.

9. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyalkylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid, and a pigment, in the presence of an alcoholic compound containing in its molecule at least 10 carbon atoms.

10. The process for improving textile fabrics which comprises treating them in a bath containing a water-soluble salt of a polyhydroxyethylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms, said salt being formed with salicylic acid, and a pigment, in the presence of an alcoholic compound containing in its molecule at least 10 carbon atoms.

11. A process for procuring matt efiects on artificial silk which comprises treating the same in a bath containing a pigment, the salicylate of a polyhydroxyalkylated biguanide of an aliphatic base containing in its molecule at least 10 carbon atoms and an alcoholic compound containing in its molecule at least 10 carbon atoms.

. 12. The process as claimed in claim 11, wherein the said treatment is combined with the dyeing process for the fabric.

KARL BRODERSEN.

QUAEDVLIEG. MAX zaann ALBERT sci-mamas. 

